Synthesis method of a triphenylene derivative containing a triazine structure

Abstract

This application relates to the technical field of organic optoelectronic materials, and specifically discloses a synthesis method of a triphenylene derivative containing a triazine structure, which includes the following steps: (1) Under an inert atmosphere, add a halo-substituted triazine derivative, solvent I, base I, solvent B into a glass reaction flask, stir evenly, then add a biphenyl boronic halide, and then add catalyst I. After stirring evenly, add ligand I. After the reaction is completed, intermediate 1 is obtained through post-treatment; (2) Under an inert atmosphere, add intermediate 1, solvent II, base II, and a boron-containing reagent into a glass reaction flask, stir evenly, then add catalyst II and ligand II. After the reaction is completed, it is obtained through post-treatment; This application provides a synthesis method of a triphenylene derivative containing a triazine structure. Compared with the traditional synthesis of triphenylene, this method has the characteristics of low raw material cost, simple operation steps, high yield, etc., and is suitable for rapidly constructing triphenylene compounds.

Description

Technical Field

[0001] This application relates to the technical field of organic optoelectronic materials, and more specifically, it relates to a method for synthesizing a triphenylene derivative containing a triazine structure. Background Art

[0002] The benzene ring, as the earliest discovered aromatic ring, is one of the important building blocks for constructing organic compounds. Triphenylene compounds (also known as polycyclic aromatic hydrocarbons) are a class of important π-conjugated functional materials with special optoelectronic properties. They are a new type of optoelectronic material and can be used in optoelectronic devices, optical data storage devices, photovoltaic solar cells, and light-emitting diodes (Angew. Chem. Int. Ed. 2007, 46, 4832 - 4887; Chemical Reviews, 2001, 101, 5). Therefore, this type of material has great development and utilization value.

[0003] Currently, the synthesis research of triphenylene mainly focuses on the preparation through the polycyclization reaction of arynes and the double coupling reaction of bimetallic reagents and dihaloarenes. However, the polyreaction of arynes is difficult to control. Especially for substituted aryne intermediates, a mixture of regioisomers is often obtained, which is difficult to separate. Moreover, the raw materials for generating arynes contain trifluoromethanesulfonate groups and are expensive. In addition, due to the influence of factors such as solubility and steric hindrance, the preparation of bimetallic reagents has a low yield and high preparation difficulty. The types of commercially available bimetallic reagents are limited and expensive (Angew. Chem. Int. Ed., 1998, 37, 2659;

[0004] J. Chem. Soc., Chem. Commun. 1994, 465).

[0005] Therefore, it is of great significance to develop new methods for preparing triphenylene compounds. Summary of the Invention

[0006] In order to solve the problems in the existing polyreaction of arynes, which is difficult to control. Especially for substituted aryne intermediates, a mixture of regioisomers is often obtained, which is difficult to separate. Moreover, the raw materials for generating arynes contain trifluoromethanesulfonate groups and are expensive. In addition, due to the influence of factors such as solubility and steric hindrance, the preparation of bimetallic reagents has a low yield and high preparation difficulty. The types of commercially available bimetallic reagents are limited and expensive, etc., this application provides a method for synthesizing a triphenylene derivative containing a triazine structure.

[0007] This application provides a method for synthesizing a triphenylene derivative containing a triazine structure, adopting the following technical scheme:

[0008] A method for synthesizing a triphenylene derivative containing a triazine structure, which comprises the following steps:

[0009] (1) Under an inert atmosphere, add a halo-s-triazine derivative, Solvent I, Base I, and Solvent B to a glass reaction flask. After stirring evenly, add a biphenyl boronic acid halide, then add Catalyst I. After stirring evenly, add Ligand I. After the reaction is completed, obtain Intermediate 1 through post-treatment;

[0010] (2) Under an inert atmosphere, add Intermediate 1, Solvent II, and Base II, and a boron-containing reagent to a glass reaction flask. After stirring evenly, add Catalyst II and Ligand II. After the reaction is completed, obtain the product through post-treatment.

[0011] Preferably, the reaction equation of the synthesis method is as follows:

[0012]

[0013] In the formula: R1 and R2 are aromatic rings and their derivatives, and R1 and R2 are the same or different;

[0014] X is chlorine, bromine, or iodine; Y is chlorine or iodine; X and Y are the same or different.

[0015] Preferably, in the step (1), Solvent I is selected from at least one of chloroform, 1,1-dichloroethane, tetrahydrofuran, 1,4-dioxane, chlorobenzene, toluene, and decalin.

[0016] Preferably, in the step (1), Base I is selected from at least one of potassium acetate, potassium carbonate, sodium carbonate, sodium bicarbonate, and Lewis base.

[0017] Preferably, in the step (1), Solvent B is selected from at least one of methanol, ethanol, ethylene glycol, tert-butanol, acetone, and butanone.

[0018] Preferably, in the step (1), the biphenyl boronic acid halide is selected from at least one of 2-chloro-2-biphenyl boronic acid, 2-iodo-2-biphenyl boronic acid, 2-iodo-2-boronic acid-4,4'-dimethylbiphenyl, 2-chloro-2-boronic acid-4,4'-dimethylbiphenyl, and 2-iodo-2-boronic acid-4,4'-dimethoxybiphenyl.

[0019] Preferably, in the step (1), Catalyst I is selected from at least one of palladium acetate, palladium chloride, palladium trifluoroacetate, palladium(II) bis(acetylacetonate), tris(dibenzylideneacetone) dipalladium, palladium tetrafluoroborate tetraacetonitrile, allylpalladium(II) chloride dimer, [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium, bis(triphenylphosphine) dichloropalladium, and copper bromide.

[0020] Preferably, in step (1), ligand I is selected from at least one of 2-chloro-1,3-di(2,6-diisopropylphenyl)-1,3,2-diazaphospholane, (SIPr)Ph2Pd(cin)Cl, Pd(IPr)(cinammyl)Cl, IPrCuOt-Bu, P(o-tolyl)3, BippyPhos, and 1,10-phenanthroline.

[0021] Preferably, in step (1), the molar ratio of the monohalotriazine derivative to the base I is 1:(2-5).

[0022] Preferably, in step (1), the molar ratio of the monohalogenated triazine derivative to the halogenated biphenyl borate is 1:(1-3).

[0023] Preferably, the molar ratio of the monohalogenated triazine derivative to the catalyst I in step (1) is 1:(0.001-0.01).

[0024] Preferably, the molar ratio of the monohalogenated triazine derivative to the ligand I in step (1) is 1:(0.005-0.2).

[0025] Preferably, in step (2), the solvent II is selected from at least one of xylene, toluene, N,N-dimethylformamide, N,N-dimethylacetamide, acetone and ethyl acetate.

[0026] Preferably, in step (2), the base II is selected from at least one of sodium hydroxide, trimethylethylamine, sodium tert-butoxide and potassium carbonate.

[0027] Preferably, the boron-containing reagent in step (2) is selected from at least one of boric acid pinacol ester, biboric acid pinacol ester and pinacol boron.

[0028] Preferably, in step (2), catalyst II is selected from at least one of [(NHC)Pd(η3-allyl)]2(μ2-N-heterocycles)(BF4)2, Pd(IPr)(acac)Cl, Pd(OAc)2, and SIMesCuCl.

[0029] Preferably, in step (2), ligand II is selected from at least one of tri-tert-butylphosphine, S-(-)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine, tri(o-methylphenyl)phosphine, and 4,5-bisdiphenylphosphine-9,9-dimethylxanthene.

[0030] Preferably, in step (2), the molar ratio of intermediate 1 to base II is 1:(1-5).

[0031] Preferably, in step (2), the molar ratio of intermediate 1 to the boron-containing reagent is 1:(0.8-1).

[0032] Preferably, in the step (2), the molar ratio of intermediate 1 to catalyst II is 1: (0.001 - 0.01).

[0033] Preferably, in the step (2), the molar ratio of intermediate 1 to ligand II is 1: (0.01 - 0.2).

[0034] Preferably, in the step (2), catalyst II and ligand II are first mixed evenly and then added to the reaction.

[0035] Preferably, the post-treatment operation in the step (2) is selected from at least one of quenching, extraction, recrystallization, column chromatography, and suction filtration.

[0036] In summary, the present application has the following beneficial effects:

[0037] The present application provides a method for synthesizing a triphenylene derivative containing a triazine structure. Compared with the traditional synthesis of triphenylene, this method has the characteristics of low raw material cost, simple operation steps, high yield, etc., and is suitable for rapidly constructing triphenylene compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 1H NMR spectrum of dptp - triazine prepared in Example 1 of the present application. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0039] The following further elaborates the present application in conjunction with embodiments.

[0040] Examples 1 - 9 provide a method for synthesizing a triphenylene derivative containing a triazine structure, and its synthetic route is as follows:

[0041]

[0042] Example 1

[0043] A method for synthesizing a triphenylene derivative containing a triazine structure, comprising the following steps:

[0044] (1) Synthesis of Intermediate 1: Under a nitrogen atmosphere, add 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (19.41 g, 50 mmol) to a glass reaction flask, and stir evenly with chloroform and chlorobenzene (120 ml, v / v = 1:1). Then, successively add potassium acetate (14.72 g, 150 mmol) and ethanol (30 ml). Replace the air in the reaction flask with nitrogen three times to ensure a nitrogen atmosphere in the reaction flask. Then, add 2-chloro-2-biphenylboronic acid in two batches (11.62 g, 50 mmol, 5.81 g per batch, with an interval of 10 min), and stir for 30 min. Subsequently, add palladium trifluoroacetate (0.017 g, the molar ratio of 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine to palladium trifluoroacetate is 1:0.001). After stirring at room temperature for 1 h, raise the temperature to 40 °C. Then, add 2-chloro-1,3-bis(2,6-diisopropylphenyl)-1,3,2-diazaphospholane (0.11 g, 0.25 mmol) and continue stirring. At this time, introduce nitrogen into the reaction system, raise the temperature to 80 °C, and stir for 12 h. Continuously introduce nitrogen throughout the reaction process until the reaction is completed. After the reaction solution returns to room temperature, pour the reaction solution into ice water, stir for 30 min, and filter by suction. Wash the obtained upper-layer filter cake with methanol (50 ml each time, wash 3 times) to obtain the crude product of Intermediate 1. Purify the obtained crude product of Intermediate 1 by column chromatography, using ethyl acetate and petroleum ether as eluents (v / v = 1:7). Collect the eluent containing Intermediate 1, evaporate the organic solvent by rotary evaporation, and obtain the pure product of Intermediate 1 (21.57 g, yield 86%, purity 98.6%) after drying.

[0045] (2) Synthesis of dptp-triazine: In a nitrogen atmosphere, intermediate 1 (24.8 g, 50 mmol) and xylene (200 ml) were added to a glass reaction bottle and stirred evenly, and then trimethylethylamine (5.05 g, 50 mmol) and boric acid pinacol ester (6.7 g, 45 mmol) were added at 0°C and stirred continuously to form a mixed solution. Xylene (20 ml), Pd(IPr)(acac)Cl (0.094 g, 0.15 mmol) and tri-tert-butylphosphine (0.114 g, 0.5 mmol) were added to another reaction bottle and stirred evenly, and then added dropwise (dropping rate 10 ml / min) to the mixed solution containing intermediate 1. Reflux reaction for 10h, then add ethanol (100ml) to quench, after the reaction solution returns to room temperature, pour into acetone (200ml) and stir for 10min, filter with suction, and wash the upper filter cake with petroleum ether (100ml each time, wash twice) to obtain crude dptp-triazine. The obtained crude product is added to a mixed solvent of toluene and ethanol (2L, v / v=1:1) for recrystallization for 30min, then filtered with suction, and dried to obtain pure dptp-triazine (20.68g, yield 90%, purity 99.4%).

[0046] Example 2

[0047] Compared with Example 1, only the 2-chloro-2-boronic acid biphenyl in step (1) was replaced with 2-iodo-2-boronic acid biphenyl, and the other steps remained unchanged to obtain intermediate 1 (19.47 g, yield 77%, purity 95%); finally, pure dptp-triazine (19.53 g, yield 85%, purity 97.4%) was obtained.

[0048] Example 3

[0049] Compared with Example 1, only the potassium acetate in step (1) was replaced with sodium bicarbonate, and the other steps remained unchanged to obtain intermediate 1 (15.6 g, yield 62%, purity 95.3%); finally, pure dptp-triazine (19.99 g, yield 87%, purity 97.9%) was obtained.

[0050] Example 4

[0051] Compared with Example 1, only the palladium trifluoroacetate in step (1) was replaced with copper bromide, and the other steps remained unchanged to obtain intermediate 1 (21.82 g, yield 87%, purity 97.4%); finally, pure dptp-triazine (20.22 g, yield 88%, purity 99%) was obtained.

[0052] Example 5

[0053] Compared with Example 1, only the 2-chloro-1,3-di(2,6-diisopropylphenyl)-1,3,2-diazaphospholane in step (1) was changed to 1,10-phenanthroline, and the other steps remained unchanged to obtain intermediate 1 (21.32 g, yield 85%, purity 98.7%); finally, pure dptp-triazine (20.68 g, yield 90%, purity 99.4%) was obtained.

[0054] Example 6

[0055] Compared with Example 1, only trimethylethylamine in step (2) was replaced by sodium tert-butoxide, and the other steps remained unchanged to obtain pure dptp-triazine (20.68 g, yield 90%, purity 99.1%).

[0056] Example 7

[0057] Compared with Example 1, only the pinacol borate in step (2) was replaced by pinacol diborate, and the other steps remained unchanged to obtain pure dptp-triazine (19.53 g, yield 85%, purity 98.7%).

[0058] Example 8

[0059] Compared with Example 1, only the tri-tert-butylphosphine in step (2) was replaced with 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, and the other steps remained unchanged to obtain pure dptp-triazine (19.99 g, yield 87%, purity 99.2%).

[0060] Example 9

[0061] Compared with Example 1, only Pd(IPr)(acac)Cl in step (2) was replaced by SIMesCuCl, and the other steps remained unchanged to obtain dptp-triazine (19.30 g, yield 84%, purity 99.4%).

[0062] Comparative Example 1

[0063] Compared with Example 1, only the order of adding catalyst II and ligand II in (2) is changed, that is, catalyst II is added first, and then ligand II is added. The specific operation is as follows:

[0064] (2) Synthesis of dptp-triazine: Under nitrogen atmosphere, intermediate 1 (24.8 g, 50 mmol) and xylene (200 ml) were added to a glass reaction bottle and stirred evenly. Then, trimethylethylamine (5.05 g, 50 mmol) and boric acid pinacol ester (6.7 g, 45 mmol) were added at 0°C and stirred continuously to form a mixed solution. Take another reaction bottle, add xylene (10ml), Pd (IPr) (acac) Cl (0.094g, 0.15mmol) and stir evenly, then add dropwise (drop rate 10ml / min) to the mixed solution containing intermediate 1, add tri-tert-butylphosphine (0.114g, 0.5mmol) after the addition is complete, reflux for 10h, then add ethanol (100ml) to quench, after the reaction solution returns to room temperature, pour into acetone (200ml) and stir for 10min, filter, and wash the upper filter cake with petroleum ether (100ml each time, wash twice) to obtain crude dptp-triazine. The obtained crude product is added to a mixed solvent of toluene and ethanol (2L, v / v=1:1) for recrystallization for 30min, then filtered and dried to obtain pure dptp-triazine (18.62g, yield 81%, purity 98.1%).

[0065] Comparative Example 2

[0066] Compared with Example 1, only the order of adding catalyst II and ligand II in (2) is changed, ligand II is added first, and then catalyst II is added. The specific operation is as follows:

[0067] (2) Synthesis of dptp-triazine: Under nitrogen atmosphere, intermediate 1 (24.8 g, 50 mmol) and xylene (200 ml) were added to a glass reaction bottle and stirred evenly. Then, trimethylethylamine (5.05 g, 50 mmol) and boric acid pinacol ester (6.7 g, 45 mmol) were added at 0°C and stirred continuously to form a mixed solution. Take another reaction bottle, add xylene (10ml), tri-tert-butylphosphine (0.114g, 0.5mmol) and stir evenly, then add dropwise (drop rate 10ml / min) to the mixed solution containing intermediate 1, add Pd(IPr)(acac)Cl (0.094g, 0.15mmol) after the addition is complete, reflux reaction for 10h, then add ethanol (100ml) to quench, after the reaction solution returns to room temperature, pour into acetone (200ml) and stir for 10min, filter, and wash the upper filter cake with petroleum ether (100ml each time, wash twice) to obtain crude dptp-triazine. The obtained crude product is added to a mixed solvent of toluene and ethanol (2L, v / v=1:1) for recrystallization for 30min, then filtered and dried to obtain pure dptp-triazine (17.7g, yield 77%, purity 94.9%).

[0068] This specific embodiment is only an interpretation of the present application and does not limit the present application. After reading this specification, those skilled in the art can make modifications to this embodiment that do not contribute creatively as needed, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A method for synthesizing a triphenylene derivative containing a triazine structure, characterized in that, The steps include: (1) In an inert atmosphere, a halogenated triazine derivative, solvent I, base I, and solvent B are added to a glass reaction bottle, and after stirring, a halogenated biphenyl borate is added, and then a catalyst I is added, and after stirring, a ligand I is added. After the reaction is completed, an intermediate 1 is obtained by post-treatment; (2) In an inert atmosphere, intermediate 1, solvent II, base II, and boron-containing reagent are added to a glass reaction bottle, and after stirring, catalyst II and ligand II are added. After the reaction is completed, post-treatment is performed to obtain; The reaction equation of the synthesis method is as follows: In the formula: R1 and R2 are aromatic rings and their derivatives, and R1 and R2 are the same or different; X is chlorine, bromine or iodine; Y is chlorine or iodine; X and Y are the same or different; In the step (1), the base I is potassium acetate or sodium bicarbonate; In the step (1), the halogenated biphenyl borates are 2-chloro-2-biphenyl borates or 2-iodo-2-biphenyl borates; In the step (1), the catalyst I is palladium trifluoroacetate or copper bromide; In the step (1), the ligand I is 2-chloro-1,3-di(2,6-diisopropylphenyl)-1,3,2-diazaphospholane or 1,10-phenanthroline; In the step (2), the base II is trimethylethylamine or sodium tert-butoxide; The boron-containing reagent in step (2) is pinacol borate or pinacol diborate; In the step (2), the catalyst II is Pd(IPr)(acac)Cl or SIMesCuCl; In the step (2), the ligand II is selected from tri-tert-butylphosphine or 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene.

2. The method for synthesizing a triphenylene derivative containing a triazine structure according to claim 1, characterized in that, In the step (1), the molar ratio of the monohalogenated triazine derivative to the base I is 1:(2-5); the molar ratio of the monohalogenated triazine derivative to the halogenated biphenyl borate is 1:(1-3); the molar ratio of the monohalogenated triazine derivative to the catalyst I is 1:(0.001-0.01); and the molar ratio of the monohalogenated triazine derivative to the ligand I is 1:(0.005-0.2).

3. The method for synthesizing a triphenylene derivative containing a triazine structure according to claim 1, characterized in that, In the step (2), the molar ratio of intermediate 1 to base II is 1:(1-5); the molar ratio of intermediate 1 to boron-containing reagent is 1:(0.8-1); the molar ratio of intermediate 1 to catalyst II is 1:(0.001-0.01); and the molar ratio of intermediate 1 to ligand II is 1:(0.01-0.2).

4. The method for synthesizing a triphenylene derivative containing a triazine structure according to claim 1, characterized in that, The post-treatment operation in step (2) is selected from at least one of quenching, extraction, recrystallization, column chromatography, and filtration.

Images